CN113384744B - WS2 nanosheet/bioglass microsphere composite material and preparation method thereof - Google Patents
WS2 nanosheet/bioglass microsphere composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a WS2A nano-sheet/biological glass microsphere composite material and a preparation method thereof. Preparation of thin layer WS by liquid phase ultrasonic stripping method2Nanosheet, preparing bioglass microspheres by combining a sol-gel method with a liquid template method, and finally preparing WS by adopting an ultrasonic method2A nano-sheet/biological glass microsphere composite material. The invention utilizes the action of ultrasound to lead WS to2Nanosheet and bioglass microsphere compositeThe method has strong controllability and simple operation. WS in the invention2The binding force of the nanosheet and the bioglass microspheres is strong, the components are uniformly distributed, the process is simple, and the cost is low. Due to the prepared WS2The nano-sheet/biological glass microsphere composite material has near infrared photothermal property, thereby showing excellent antibacterial property. And because the composite material has high specific surface area, the composite material can rapidly induce the generation of apatite precipitate in body fluid and has high biological activity. The invention has great industrialization prospect and medical application value.
Description
Technical Field
The invention belongs to the field of biomedical materials, and particularly relates to WS2A nano-sheet/biological glass microsphere composite material and a preparation method thereof.
Background
With the increase of the average life of people, the aging problem of the world population is increasingly serious, the incidence rate of orthopedic diseases is increased year by year, and the clinical demand of bone defect repair products is also increased. At present, natural bone grafting and artificial bone repairing materials are mainly used as treatment means for bone tissue repair and reconstruction clinically. The artificial bone repair material has wide sources and various varieties, not only overcomes the defect of limited self bone material acquisition, but also avoids the danger of immunological rejection reaction and disease source transmission after allogeneic bone transplantation, and some materials with biological activity can act with osteoblasts in vivo after being implanted into the body to promote osteogenesis, and has achieved great success in clinical application in recent years.
The artificial bone repair material is mainly divided into inorganic materials, organic polymer materials and composite materials. Among them, inorganic nonmetallic materials having a composition similar to bone minerals have exhibited excellent bone tissue repair functions. The artificially synthesized inorganic non-metallic bone repair material is mainly represented by bioglass, which has high biological activity, is degradable and is safe and nontoxic to human bodies, so that the bioglass is widely concerned in related fields.
Bioglass has been studied for over fifty years and has been used clinically for over twenty years for the repair of bone defects. It was first applied for the repair of hard bone tissue, and more studies in recent years have demonstrated that it can also be used for the repair of cartilage and soft tissues, such as skin, cornea, lung, nervous tissue, etc.
The sol-gel method is combined with the template method to prepare the bioglass microspheres with regular shapes. The template method is characterized in that a surfactant is used as a structure guiding template, an inorganic precursor and the template are subjected to self-assembly in a solution to form a specific morphological structure, and finally the template is removed through sintering to obtain the micro-nano bioactive glass with regular morphology and controllable size. Compared with the traditional sol-gel method, the sol-gel method is combined with the template method to prepare the bioglass microspheres with higher bioactivity and monodispersity, and the shape, the size and the structure of the micro-nano bioglass can be regulated and controlled by changing the using amount of the template agent.
Although the bioglass microspheres have good bioactivity, the bioglass microspheres also face practical problems when used alone. Because the specific surface area of the bioglass powder is still lower, the contact area with water molecules is smaller, and thus the bioactivity is influenced. In order to overcome this problem, the combination of bioglass with polymeric and semiconducting materials and the preparation of composite materials is expected to solve the above problems.
WS2The nano sheet is a semiconductor nano material, has a graphene-like sandwich structure, has become a focus of material science interest in recent years, and has a very good application prospect in many fields including nano medicine. WS2The nano-sheet has the advantages of super-high specific surface area, excellent fluorescence quenching capability, sensitive photoelectric response characteristic, good biocompatibility, higher hydrophilicity and near infrared photothermal property. WS2The nanosheet has an energy band gap of 1-2 eV, so that it has excellent near-infrared light absorption characteristics, and is widely used for research on photothermal therapy. WS2The extinction coefficient of the nano-sheet at 808 nm is 23.8 Lg-1cm-1Higher than graphene oxide, WS has been used by some people2The characteristics of the nano-sheet produce a composite therapeutic reagent which is applied to the photo-thermal treatment of cancer cells. Photothermal therapyWhen WS is outside2After the nano sheet is irradiated by near infrared light, the temperature can be rapidly raised to 75 ℃ in 10-20 min, the nano sheet has an obvious antibacterial effect on bacteria which are not high in temperature resistance, and when the bacteria and WS are irradiated2When the nanoplates are in proximity, WS2Sharp edges tend to disrupt the structure of the bacterial membrane, and therefore WS2Exhibit excellent antibacterial properties. WS2The nano-sheet has higher hydrophilicity, specific surface area and good biocompatibility, can promote ion exchange between bioglass and body fluid, accelerate generation of apatite precipitate, and thus contribute to improving bioactivity of bioglass microspheres, but related WS2The nano-sheet/biological glass microsphere composite material is not reported yet.
Disclosure of Invention
WS (WS)2The preparation method of the nano-sheet/biological glass microsphere composite material comprises the following steps:
(1) preparation of WS by liquid phase ultrasonic stripping2Nanosheet: selecting block WS2Preparing 4 mg/ml solution as raw material, and adding block WS2Ultrasonic stripping of bulk WS from tannic acid of equal mass2Treating the supernatant to obtain WS2Nanosheets;
(2) preparing the bioglass microspheres by combining a sol-gel method with a liquid template method: sequentially adding 0.7 g of hexadecyl trimethyl ammonium bromide, 10 ml of ethyl acetate, 7 ml of ammonia water (concentration: 1 mol/L), 3.6 ml of tetraethyl orthosilicate, 0.85 ml of triethyl phosphate and 1.964 g of calcium nitrate tetrahydrate into a reaction container, uniformly stirring to fully dissolve various reagents to form white suspension, centrifuging to obtain white gel, and calcining in a muffle furnace to obtain bioglass microsphere powder;
(3) finally, the obtained WS is treated under the action of ultrasound2Compounding the nano sheets and the bioglass microspheres according to different mass ratios to prepare a plurality of groups of samples with different mass ratios, centrifuging and taking precipitates to obtain WS2A nano-sheet/biological glass microsphere composite material.
In the step (1), ultrasonic power of 400-600W, frequency of 40 KHz and ultrasonic treatment time of 1-3 h are selected by ultrasonic stripping treatment.
After ultrasonic stripping treatment in the step (1), centrifuging to extract supernatant, wherein the centrifugal speed is 4000 r/min, centrifuging and washing three times at 9000 r/min to obtain precipitate, and centrifuging for 5 min each time to obtain thin layer WS2Nanosheets.
In the process of preparing the bioglass microspheres in the step (2), stirring is carried out for 30 min after the reagent is added each time, the next reagent is added after the reagent is uniformly stirred, and stirring is carried out for 3h after all the reagents are added.
And (3) centrifuging the white suspension in the step (2) at the rotating speed of 7000 r/min for 3min, taking out a precipitate after centrifugation, and repeatedly washing the precipitate for three times at the speed of 7000 r/min to obtain white gel.
And (3) drying the white gel in the step (2) before calcining, wherein the drying temperature is 60 ℃, the drying time is 24 hours, and after drying, the sample needs to be ground into powder and then calcined.
Step (3) WS2Compounding nano sheet and biological glass microsphere in different weight proportion, WS2: bioglass =x：100-x (x=1 to 40); the required ultrasonic power is 400-600W, the frequency is 40 KHz, and the ultrasonic treatment time is 1-2 h.
Centrifuging to obtain WS in step (3)2When the nano-sheet/biological glass microsphere composite material is prepared, the centrifugal rotating speed is 7000 r/min, and the time is 5 min.
The invention has the following remarkable advantages:
1. the present invention utilizes the effect of ultrasound to obtain WS2The composite material obtained by centrifuging, cleaning and drying the nanosheet/bioglass composite material has uniform size, simple preparation process, low cost of raw materials and short time consumption, and is used for preparing WS in a large scale2The method of the nano-sheet/biological glass composite material has important industrialization prospect.
2. WS prepared according to the invention2The nano-sheet/biological glass microsphere composite material has near infrared photothermal property, and WS2The sharp edge easily destroys the structure of the bacterial membrane, and thus exhibits excellent antibacterial properties. And the composite material has high specific surface area and is fast in body fluidQuickly inducing the generation of apatite precipitate and having high bioactivity. The invention has wide medical application value.
3. Compared with graphene/bioglass microsphere composite material, WS according to Bill-Lambert's law2The extinction coefficient of the nano sheet is 23.8 lg-1cm-1While graphene is only 3.6 lg-1cm-1This indicates WS2The nano-sheet has stronger absorption characteristic and photothermal conversion efficiency in a first near-infrared biological window. Thus, in terms of antibacterial properties, WS2The nano-sheet/biological glass microsphere composite material can cause bacterial death by high temperature generated after 808 nm infrared illumination, and the graphene/biological glass microsphere composite material can not generate a large amount of heat to cause bacterial death, so WS2The nano-sheet/biological glass microsphere composite material shows excellent antibacterial property.
Drawings
FIG. 1 shows WS according to the present invention2A flow schematic diagram of the nano sheet/biological glass microsphere composite material;
FIG. 2 shows WS obtained in example 32Biological glass microsphere composite material and undoped WS2The XRD pattern of the bioglass of (a);
FIG. 3 is an SEM image of bioglass microspheres obtained by a sol-gel combined liquid template method in example 3;
FIG. 4 shows WS obtained by liquid phase ultrasonic exfoliation method in example 32SEM images of the nanoplatelets;
FIG. 5 shows WS prepared in example 32SEM image of the nanoplate/bioglass composite;
FIG. 6 shows undoped WS prepared in example 32SEM images of bioglass (g) soaked in simulated body fluid SBF for 7 days;
FIG. 7 is an SEM image of a graphene/bioglass composite material prepared by a comparative example soaked in simulated body fluid SBF for 7 days;
FIG. 8 shows WS prepared in example 32SEM images of the nanosheet/bioglass composite mineralized in simulated body fluid SBF for 7 days;
FIG. 9 is a graph showing the antibacterial effect of the present invention without sample culture;
FIG. 10 is a graph showing the antibacterial effect of the graphene/bioglass composite material prepared in the comparative example, which is cultured after being irradiated by 808 nm infrared light;
FIG. 11 shows WS prepared in example 32An antibacterial effect diagram of the nano-sheet/bioglass composite material cultured after 808 nm infrared light irradiation.
Detailed Description
The present invention provides a WS2The preparation method of the nano-sheet/biological glass microsphere composite material is further detailed below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
WS (WS)2The preparation method of the nano-sheet/biological glass microsphere composite material comprises the following steps:
preparation of WS by liquid phase ultrasonic stripping2Nanosheets, wherein the bulk WS is selected2Preparing 4 mg/ml solution as raw material, and adding block WS2Ultrasonic stripping of bulk WS from tannic acid of equal mass2Treating the supernatant to obtain WS2Nanosheets. The bioglass microsphere is prepared by combining a sol-gel method with a liquid template method, 0.7 g of hexadecyl trimethyl ammonium bromide, 10 ml of ethyl acetate, 7 ml of ammonia water (concentration: 1 mol/L), 3.6 ml of tetraethyl orthosilicate, 0.85 ml of triethyl phosphate and 1.964 g of calcium nitrate tetrahydrate are sequentially added into a reaction container and uniformly stirred, so that various reagents are fully dissolved to form white turbid liquid, the white turbid liquid is centrifuged to obtain white gel, and the white gel is calcined in a muffle furnace to obtain bioglass microsphere powder. Finally, the obtained WS is treated under the action of ultrasound2Compounding nano sheet and biological glass microsphere in certain proportion, centrifuging to obtain precipitate and obtain WS2A nano-sheet/biological glass microsphere composite material.
The ultrasonic power is 400W, the frequency is 40 KHz, and the ultrasonic processing time is 1 h.
Ultrasonic ablationAfter treatment, the supernatant fluid is extracted by centrifugation, wherein the centrifugal speed is 4000 r/min, and the precipitate is obtained by three times of centrifugal washing at 9000 r/min, and the centrifugation time is 5 min each time, thus obtaining the thin layer WS2Nanosheets.
In the process of preparing the bioglass microspheres, the reagent is added each time and then stirred for 30 min, the next reagent is added after the reagent is uniformly stirred, and the stirring is carried out for 3h after all the reagents are added.
Centrifuging the white suspension at 7000 r/min for 3min, collecting precipitate, and repeatedly washing at 7000 r/min for three times to obtain white gel.
The white gel needs to be dried before calcination, the drying temperature is 60 ℃, the drying time is 24 hours, and after drying, the sample needs to be ground into powder and then calcined.
Let WS be2Compounding nano sheet and biological glass microsphere in certain weight proportion, WS2: bioglass =x：100-x (x= 1); the required ultrasonic power is 400W, the frequency is 40 KHz, and the ultrasonic processing time is 1 h.
Centrifugal WS2When the nano-sheet/biological glass microsphere composite material is prepared, the centrifugal rotating speed is 7000 r/min, and the time is 5 min.
Example 2
WS (WS)2The preparation method of the nano-sheet/biological glass microsphere composite material comprises the following steps:
preparation of WS by liquid phase ultrasonic stripping2Nanosheets, wherein the bulk WS is selected2Preparing 4 mg/ml solution as raw material, and adding block WS2Ultrasonic stripping of bulk WS from tannic acid of equal mass2Treating the supernatant to obtain WS2A nanosheet. Preparing bioglass microspheres by combining a sol-gel method with a liquid template method, sequentially adding 0.7 g of hexadecyl trimethyl ammonium bromide, 10 ml of ethyl acetate, 7 ml of ammonia water (concentration: 1 mol/L), 3.6 ml of tetraethyl orthosilicate, 0.85 ml of triethyl phosphate and 1.964 g of calcium nitrate tetrahydrate into a reaction container, uniformly stirring to fully dissolve various reagents to form white suspension, centrifuging to obtain white gel, and adding the white gel into the reaction container until the mixture is completely dissolved to obtain the bioglass microspheresCalcining in a muffle furnace to obtain the bioglass microsphere powder. Finally, the obtained WS is treated under the action of ultrasound2Compounding nano sheet and biological glass microsphere in certain proportion, centrifuging to obtain precipitate and obtain WS2A nano-sheet/biological glass microsphere composite material.
Ultrasonic power of 500W, frequency of 40 KHz and ultrasonic treatment time of 2 h are selected by ultrasonic stripping treatment.
Centrifuging to extract supernatant after ultrasonic stripping at 4000 r/min, centrifuging at 9000 r/min for three times (each time for 5 min) to obtain thin layer WS2A nanosheet.
In the process of preparing the bioglass microspheres, the reagent is added each time and then stirred for 30 min, the next reagent is added after the reagent is uniformly stirred, and the reagent is stirred for 3h after all the reagents are added.
Centrifuging the white suspension at 7000 r/min for 3min, collecting precipitate, and repeatedly washing at 7000 r/min for three times to obtain white gel.
The white gel needs to be dried before calcination, the drying temperature is 60 ℃, the drying time is 24 hours, and after drying, the sample needs to be ground into powder and then calcined.
Let WS be2Compounding nano sheet and biological glass microsphere in certain weight proportion, WS2: bioglass =x：100-x (x= 10); the required ultrasonic power is 500W, the frequency is 40 KHz, and the ultrasonic processing time is 1 h.
Centrifugal WS2When the nano-sheet/biological glass microsphere composite material is prepared, the centrifugal rotating speed is 7000 r/min, and the time is 5 min.
Example 3
WS (WS)2The preparation method of the nano-sheet/biological glass microsphere composite material comprises the following steps:
preparation of WS by liquid phase ultrasonic stripping2Nanosheets, wherein the bulk WS is selected2Preparing 4 mg/ml solution as raw material, and adding block WS2Ultrasonic stripping of bulk WS from tannic acid of equal mass2Treatment ofTaking the supernatant to obtain WS2Nanosheets. The bioglass microsphere is prepared by combining a sol-gel method with a liquid template method, 0.7 g of hexadecyl trimethyl ammonium bromide, 10 ml of ethyl acetate, 7 ml of ammonia water (concentration: 1 mol/L), 3.6 ml of tetraethyl orthosilicate, 0.85 ml of triethyl phosphate and 1.964 g of calcium nitrate tetrahydrate are sequentially added into a reaction container and uniformly stirred, so that various reagents are fully dissolved to form white turbid liquid, the white turbid liquid is centrifuged to obtain white gel, and the white gel is calcined in a muffle furnace to obtain bioglass microsphere powder. Finally, the obtained WS is treated under the action of ultrasound2Compounding nano sheet and biological glass microsphere in certain proportion, centrifuging to obtain precipitate and obtain WS2A nano-sheet/biological glass microsphere composite material.
Ultrasonic power of 600W, frequency of 40 KHz and ultrasonic treatment time of 3h are selected by ultrasonic stripping treatment.
Centrifuging to extract supernatant after ultrasonic stripping at 4000 r/min, centrifuging at 9000 r/min for three times (each time for 5 min) to obtain thin layer WS2Nanosheets.
In the process of preparing the bioglass microspheres, the reagent is added each time and then stirred for 30 min, the next reagent is added after the reagent is uniformly stirred, and the reagent is stirred for 3h after all the reagents are added.
Centrifuging the white suspension at 7000 r/min for 3min, collecting precipitate, and repeatedly washing at 7000 r/min for three times to obtain white gel.
The white gel needs to be dried before calcination, the drying temperature is 60 ℃, the drying time is 24 hours, and after drying, the sample needs to be ground into powder and then calcined.
Let WS be2Compounding nano sheet and biological glass microsphere in certain weight proportion, WS2: bioglass =x：100-x (x= 20); the required ultrasonic power is 600W, the frequency is 40 KHz, and the ultrasonic processing time is 2 h.
Centrifugal WS2When the nano-sheet/biological glass microsphere composite material is prepared, the centrifugal rotating speed is 7000 r/min, and the time is 5 min.
Example 4
WS (WS)2The preparation method of the nano-sheet/biological glass microsphere composite material comprises the following steps:
preparation of WS by liquid phase ultrasonic stripping2Nanosheets, wherein the bulk WS is selected2Preparing 4 mg/ml solution as raw material, and adding block WS2Ultrasonic stripping of bulk WS from tannic acid of equal mass2Treating the supernatant to obtain WS2Nanosheets. The bioglass microsphere is prepared by combining a sol-gel method with a liquid template method, 0.7 g of hexadecyl trimethyl ammonium bromide, 10 ml of ethyl acetate, 7 ml of ammonia water (concentration: 1 mol/L), 3.6 ml of tetraethyl orthosilicate, 0.85 ml of triethyl phosphate and 1.964 g of calcium nitrate tetrahydrate are sequentially added into a reaction container and uniformly stirred, so that various reagents are fully dissolved to form white turbid liquid, the white turbid liquid is centrifuged to obtain white gel, and the white gel is calcined in a muffle furnace to obtain bioglass microsphere powder. Finally, the obtained WS is treated under the action of ultrasound2Compounding nano sheet and biological glass microsphere in certain proportion, centrifuging to obtain precipitate and obtain WS2A nano-sheet/biological glass microsphere composite material.
Ultrasonic power of 600W, frequency of 40 KHz and ultrasonic treatment time of 3h are selected by ultrasonic stripping treatment.
Centrifuging to extract supernatant after ultrasonic stripping at 4000 r/min, centrifuging at 9000 r/min for three times (each time for 5 min) to obtain thin layer WS2Nanosheets.
In the process of preparing the bioglass microspheres, the reagent is added each time and then stirred for 30 min, the next reagent is added after the reagent is uniformly stirred, and the reagent is stirred for 3h after all the reagents are added.
Centrifuging the white suspension at 7000 r/min for 3min, collecting precipitate, and repeatedly washing at 7000 r/min for three times to obtain white gel.
The white gel needs to be dried before calcination, the drying temperature is 60 ℃, the drying time is 24 hours, and after drying, the sample needs to be ground into powder and then calcined.
Let WS be2Compounding nano sheet and biological glass microsphere in certain weight proportion, WS2: bioglass =x：100-x (x= 40); the required ultrasonic power is 600W, the frequency is 40 KHz, and the ultrasonic processing time is 2 h.
Centrifugal WS2When the nano-sheet/biological glass microsphere composite material is prepared, the centrifugal rotating speed is 7000 r/min, and the time is 5 min.
TABLE 1 WS with different doping ratios2Composition table of nano-sheet/biological glass microsphere composite material
Comparative example
A preparation method of a graphene/bioglass microsphere composite material comprises the following steps:
the bioglass microsphere is prepared by combining a sol-gel method with a liquid template method, 0.7 g of hexadecyl trimethyl ammonium bromide, 10 ml of ethyl acetate, 7 ml of ammonia water (concentration: 1 mol/L), 3.6 ml of tetraethyl orthosilicate, 0.85 ml of triethyl phosphate and 1.964 g of calcium nitrate tetrahydrate are sequentially added into a reaction container and uniformly stirred, so that various reagents are fully dissolved to form white turbid liquid, the white turbid liquid is centrifuged to obtain white gel, and the white gel is calcined in a muffle furnace to obtain bioglass microsphere powder. And finally, compounding the graphene (purchased) and the bioglass microspheres in proportion under the action of ultrasound, and centrifuging to obtain a precipitate to obtain the graphene/bioglass microsphere composite material.
In the process of preparing the bioglass microspheres, the reagent is added each time and then stirred for 30 min, the next reagent is added after the reagent is uniformly stirred, and the reagent is stirred for 3h after all the reagents are added.
Centrifuging the white suspension at 7000 r/min for 3min, collecting precipitate, and repeatedly washing at 7000 r/min for three times to obtain white gel.
The white gel needs to be dried before calcination, the drying temperature is 60 ℃, the drying time is 24 hours, and after drying, the sample needs to be ground into powder and then calcined.
Compounding graphene and biological glass microspheres, wherein the compounding comprises the following steps of (by mass): bioglass = 20: 80; the required ultrasonic power is 600W, the frequency is 40 KHz, and the ultrasonic processing time is 2 h.
And when the graphene/biological glass microsphere composite material is obtained through centrifugation, the centrifugation rotating speed is 7000 r/min, and the time is 5 min.
From the XRD results of FIG. 2, WS2Nanosheet/bioglass microsphere composite material existing WS2The diffraction peak of each crystal face of the nano sheet also keeps the amorphous characteristic peak of the bioglass, thereby indicating the WS2The nano-sheet/biological glass microsphere composite material is successfully prepared, and WS with the thickness of 1-2 nm and the observation picture of 3-52Successful preparation of nanosheets, bioglass microspheres having a diameter of about 40 nm, WS2The nano-sheet/biological glass microsphere composite material mainly uses biological glass microspheres to wrap WS2In the form of nanosheets and as WS2The doping ratio of the nano-sheets is improved, and WS is not caused2Loss of nanosheets, WS2The nano-sheet and the bioglass microsphere have strong binding force.
In order to research the biological activity of the material prepared by the invention, a prepared sample of 0.1 g is soaked in 20 ml of simulated body fluid SBF, the temperature is kept at 37 ℃, the simulated body fluid is replaced once every 2 days, and the biological activity of the material is judged by observing the deposition amount and the morphology of hydroxyapatite generated on the surface of the material after soaking for 7 days. By comparing FIG. 6, FIG. 7 and FIG. 8, it can be seen from the observation of FIG. 6 that WS is undoped2After the bioglass microspheres are soaked in simulated body fluid SBF for 7 days, flaky hydroxyapatite precipitates are generated on the surfaces of the bioglass microspheres, large pores exist among the hydroxyapatite precipitates, the deposition amount is small, after the graphene/bioglass microsphere composite material shown in figure 7 is mineralized in the simulated body fluid SBF for 7 days, the hydroxyapatite is not obviously changed, and WS in figure 8 is2After the nano-sheet/bioglass microsphere composite material is mineralized in simulated body fluid SBF for 7 days, the precipitation amount and density of hydroxyapatite are greatly improved, the phenomenon of piling up to form balls occurs, and the morphology of the hydroxyapatite precipitate is converted from a sheet shape to a flower sheet shape. Therefore, WS can be illustrated2Nano sheet/biological glass microsphere compositeThe biological activity of the material is obviously superior to that of the graphene/biological glass microsphere composite material and the biological glass microsphere.
To investigate the antibacterial properties of the samples prepared according to the present invention, 10 mg of the sterilized prepared sample was added to 0.9 ml of LB medium, and 0.1 ml of 108cfu/ml of Staphylococcus aureus, incubated at 37 ℃ for 6 h. The mixed solution is then diluted 104And (4) carrying out 808 nm infrared lamp light irradiation for 20 min, incubating for 24 h under the dark condition of 37 ℃ after irradiation is finished, observing the growth condition of the bacterial colony, and calculating. Comparing fig. 9, fig. 10 and fig. 11, and comparing the graphene/bioglass microsphere composite of fig. 10 with the culture medium without the sample of fig. 9, it was found that the graphene/bioglass microsphere composite did not exhibit antibacterial effect, while WS of fig. 112After the nano-sheet/biological glass microsphere composite material is subjected to 808 nm infrared illumination, almost all bacteria die under the action of a large amount of heat, so that the nano-sheet/biological glass microsphere composite material has excellent antibacterial property.
WS prepared according to the invention2The nano-sheet/biological glass microsphere composite material has near infrared photothermal property, so that excellent antibacterial property is shown. And because the composite material has high specific surface area, the composite material can rapidly induce the generation of apatite precipitate in body fluid and has high biological activity. Has wide medical application value.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (9)
1. WS (WS)2The preparation method of the nano-sheet/biological glass microsphere composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of WS by liquid phase ultrasonic stripping2Nanosheet: selecting block WS2As a raw material, a 4 mg/mL solution was prepared, and WS in bulk was added2Ultrasonic stripping of bulk WS from tannic acid of equal mass2Treating the supernatant to obtain WS2Nanosheets;
(2) preparing the bioglass microspheres by combining a sol-gel method with a liquid template method: sequentially adding 0.7 g of hexadecyl trimethyl ammonium bromide, 10 mL of ethyl acetate, 7 mL of ammonia water, 3.6 mL of tetraethyl orthosilicate, 0.85 mL of triethyl phosphate and 1.964 g of calcium nitrate tetrahydrate into a reaction container, uniformly stirring to fully dissolve various reagents to form white suspension, centrifuging to obtain white gel, and calcining in a muffle furnace to obtain bioglass microsphere powder;
(3) finally, the obtained WS is treated under the action of ultrasound2Compounding nano sheet and biological glass microsphere in different mass proportion, centrifuging to obtain precipitate and obtain WS2A nano-sheet/biological glass microsphere composite material.
2. The method of claim 1, wherein: in the step (1), ultrasonic power of 400-600W, frequency of 40 kHz and ultrasonic treatment time of 1-3 h are selected by ultrasonic stripping treatment.
3. The method of claim 1, wherein: after ultrasonic stripping treatment in the step (1), centrifuging to extract supernatant, wherein the centrifugal speed is 4000 r/min, centrifuging and washing three times at 9000 r/min to obtain precipitate, and centrifuging for 5 min each time to obtain thin layer WS2Nanosheets.
4. The method of claim 1, wherein: the concentration of the ammonia water used in the step (2) is 1 mol/L.
5. The method of claim 1, wherein: in the process of preparing the bioglass microspheres in the step (2), stirring is carried out for 30 min after the reagent is added each time, the next reagent is added after the reagent is uniformly stirred, and stirring is carried out for 3h after all the reagents are added.
6. The method of claim 1, wherein: and (3) centrifuging the white suspension in the step (2) at the rotating speed of 7000 r/min for 3min, taking out the precipitate after centrifugation, and repeatedly washing the precipitate for three times at the speed of 7000 r/min to obtain the white gel.
7. The method of claim 1, wherein: and (3) drying the white gel in the step (2) before calcining, wherein the drying temperature is 60 ℃, the drying time is 24 hours, and after drying, the sample needs to be ground into powder and then calcined.
8. The method of claim 1, wherein: step (3) WS2Compounding nano sheet and biological glass microsphere in different weight proportion, WS2: bioglass =x：100-x (x=1 to 40); the required ultrasonic power is 400-600W, the frequency is 40 kHz, and the ultrasonic treatment time is 1-2 h.
9. The method of claim 1, wherein: centrifuging to obtain WS in step (3)2When the nano-sheet/biological glass microsphere composite material is prepared, the centrifugal rotating speed is 7000 r/min, and the time is 5 min.
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